Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
  • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
  • B05D3/0209—Multistage baking
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
  • B05D7/04—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber to surfaces of films or sheets
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
  • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
  • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
  • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
  • C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/20—Diluents or solvents
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D2201/00—Polymeric substrate or laminate
  • B05D2201/02—Polymeric substrate
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D2502/00—Acrylic polymers
  • B05D2502/005—Acrylic polymers modified
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D2506/00—Halogenated polymers
  • B05D2506/10—Fluorinated polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D2518/00—Other type of polymers
  • B05D2518/10—Silicon-containing polymers
  • B05D2518/12—Ceramic precursors (polysiloxanes, polysilazanes)
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
  • B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
  • B05D3/0486—Operating the coating or treatment in a controlled atmosphere
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
  • B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
  • B05D3/061—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
  • B05D3/065—After-treatment
  • B05D3/067—Curing or cross-linking the coating
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
  • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
  • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
  • C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C08J2433/08—Homopolymers or copolymers of acrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
  • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
  • C08J2433/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
  • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
  • C08J2433/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
  • C08J2433/16—Homopolymers or copolymers of esters containing halogen atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2435/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
  • C08J2435/02—Characterised by the use of homopolymers or copolymers of esters

Definitions

• the present disclosure relates to a method of manufacturing a film.
• the resin material can be provided with features such as light weight, excellent processability, low cost, and excellent transparency. Therefore, the utility of the resin material as a glass substitute material has attracted attention in applications where glass has been mainly used conventionally.
• the surface protection film of an image display apparatus, the protective film for window glasses of a car, etc. are mentioned.
• the curable composition is made to contain a fluorine-containing compound having a perfluoroalkyl group etc., a silicon containing compound etc. having a siloxane group etc.
• films provided with resin layers such as hard coat layers and low refractive index layers have been proposed.
• reflection is obtained by sequentially laminating a hard coat layer and a low refractive index layer formed of a low refractive index layer-forming coating liquid on at least one surface of a transparent substrate.
• the low refractive index layer contains a fluorine-containing compound and a silicon-containing compound as a surface conditioner.
• a laminate having a hard coat layer formed from the curable composition is described.
• An object of an embodiment of the present invention is to provide a method for producing a film having excellent surface smoothness equal to or higher than that of glass.
• Viscosity of a solution selected from at least one of a film-forming compound, a polymer having a fluoroaliphatic group and a polymer having a siloxane structure on a support and having a solid content of 55% by mass in methyl ethyl ketone A step A of applying a coating solution containing at least a polymer having a solution temperature of 60 ° C.
• the coated film formed in step A has a mass change of not less than 0.02 g / m 2 / s and not more than 0.1 g / m 2 / s, and at least twice the t seconds satisfying the condition A shown below A step B of drying for a while and a step C of drying the coated film after step B at a rate showing a mass change of 0.02 g / m 2 / s or more and 0.2 g / m 2 / s or less Manufacturing method.
• Condition A When the dynamic surface tension of the coating liquid at a liquid temperature of 25 ° C.
• the dynamic surface tension at which the bubble lifetime is 5 seconds is ⁇ 1 and the bubble lifetime t seconds is shorter than 5 seconds. Assuming that the dynamic surface tension as such is ⁇ 2, ⁇ 2 / ⁇ 1 ⁇ 1.05 is satisfied.
• ⁇ 2> The method for producing a film according to ⁇ 1>, wherein the coating solution has a solid content concentration of 60% by mass or more.
• the ⁇ 3> process A is a manufacturing method of the film as described in ⁇ 1> or ⁇ 2> which apply
• ⁇ 5> The polymer according to any one of ⁇ 1> to ⁇ 4>, wherein the solution has a solid content of 55% by mass dissolved in methyl ethyl ketone and the viscosity of the solution is 25 mPa ⁇ s to 50 mPa ⁇ s at a liquid temperature of 60 ° C.
• the manufacturing method of the described film ⁇ 6> The method for producing a film according to any one of ⁇ 1> to ⁇ 5>, wherein the support is a continuous support.
• ⁇ 7> The method for producing a film according to any one of ⁇ 1> to ⁇ 6>, wherein the polymer comprises a polymer having a fluoroaliphatic group.
• ⁇ 8> The method for producing a film according to any one of ⁇ 1> to ⁇ 7>, wherein the coating solution contains a polymerizable compound as a film forming compound and a polymerization initiator.
• the manufacturing method of the film as described in ⁇ 8> which further includes the process D which irradiates an active energy ray to the coating film after the ⁇ 9> process C.
• the method for producing the film of the present disclosure will be described.
• the method for producing a film of the present disclosure is not limited to the embodiments described below, and can be implemented with appropriate modifications within the scope of the purpose of the present disclosure.
• the numerical range represented using “to” in the present disclosure means a range including the numerical values described before and after “to” as the lower limit value or the upper limit value.
• the upper limit value or the lower limit value described in a certain numerical value range may be replaced with the upper limit value or the lower limit value of the other stepwise description numerical value range in the numerical value range described stepwise in the present disclosure.
• the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value shown in the example.
• the amount of each component in the composition means the total amount of the plurality of substances present in the composition unless a plurality of substances corresponding to each component are present in the composition. Do.
• active energy ray includes active energy rays such as X-rays, electron beams, ultraviolet rays, visible light and infrared rays.
• (meth) acrylic acid is a concept including both acrylic acid and methacrylic acid
• (meth) acrylate is a concept including both acrylate and methacrylate
• (meth) acrylic acid” is an acryloyl group.
• a combination of two or more preferred embodiments is a more preferred embodiment.
• the method for producing a film of the present disclosure comprises at least a film-forming compound, a polymer having a fluoroaliphatic group, and a polymer having a siloxane structure on a support.
• a polymer (hereinafter also referred to as a "specified polymer”) having a viscosity of 15 mPa ⁇ s or more at 60 ° C., which is selected from one kind and dissolved in methyl ethyl ketone at a solid content of 55% by mass (hereinafter, also referred to as “specific polymer”)
• the coating film formed in step A and step A in which the coating solution containing at least the coating liquid is applied to form a coating film is subjected to mass change of 0.02 g / m 2 / s or more and 0.1 g / m 2 / s or less
• the surface smoothness of the film specifically refers to the smoothness of the surface of the resin film formed on the support by performing the steps A, B and C.
• surface smoothness equal to or higher than glass means that the light of a fluorescent lamp is projected on the outermost surface on the viewing side of the film and the reflection image of the fluorescent lamp is visually observed. This means the surface smoothness to such an extent that distortion is not visually recognized in the reflection image of the fluorescent lamp. Specifically, it can be confirmed by the following method whether a film having a support and a resin film (coated film) which is the outermost surface layer on the viewing side has the above-mentioned surface smoothness.
• the specific polymer contained in the coating liquid used in the manufacturing method of the present disclosure has a fluoroaliphatic group or a siloxane structure, and exhibits a specific viscosity, thereby causing a specific film to be dried. It is considered that the polymer is unevenly distributed on the surface of the coating film to suppress the film thickness fluctuation of the coating film and, consequently, to exhibit high smoothness on the film surface.
• step B and the step of drying the coating film are carried out.
• Step C is performed, and drying under the velocity conditions specified in step B produces a state of sufficient distribution of the specific polymer on the surface of the coating film, and further, drying of the velocity conditions specified in step C is It is speculated that by doing, excellent surface smoothness is achieved.
• Step A, Step B, Step C, and other optional steps in the production method of the present disclosure will be described.
• the production method of the present disclosure may have other steps other than the above-mentioned step A, step B and step C.
• Step A is a step of applying a coating solution containing at least a film forming compound, a specific polymer, and a solvent on a support to form a coating film.
• a resin base material can be used as a support body.
• the detail of the resin base material which can be used as a support body is mentioned later.
• the coating liquid contains at least a film forming compound, a specific polymer, and a solvent, and may contain other components as needed.
• the film-forming compound contained in the coating solution is a compound capable of forming a matrix in the resin film, includes both a polymerizable compound and a non-polymerizable resin, and is preferably a polymerizable compound.
• the film-forming compound and the specific polymer are different compounds.
• the specific polymer contained in the coating solution is a polymer having a fluoroaliphatic group or a siloxane structure, and the viscosity of a solution dissolved in methyl ethyl ketone at a solid content of 55% by mass is 15 mPa ⁇ s or more at 60 ° C.
• the solution has a viscosity of 15 mPa ⁇ s or more at a liquid temperature of 60 ° C., preferably 25 mPa ⁇ s or more and 50 mPa ⁇ s or less, and 30 mPa ⁇ s or more and 40 mPa ⁇ s. s or less is more preferable.
• the specific polymer exhibits the above-mentioned viscosity, entanglement of specific polymers occurs in the coating film, which controls the flowability of the surface of the coating film and exerts some effect on the suppression of the film thickness fluctuation.
• the viscosity is prepared by dissolving a specific polymer in methyl ethyl ketone at a solid content of 55% by mass, and measuring the viscosity at a liquid temperature of 60 ° C. using a viscometer.
• Viscosity in the present disclosure is a measurement value measured at a shear rate of 50 s ⁇ 1 using an electromagnetic spinning method.
• an EMS viscometer “EMS-1000” manufactured by Kyoto Denshi Kogyo Co., Ltd. can be used as the measuring device.
• the solid content concentration of the coating solution is preferably 60% by mass or more, more preferably 65% by mass to 90% by mass, and still more preferably 70% by mass to 80% by mass.
• the solid content concentration of the coating solution is 60% by mass or more, a film having more excellent surface smoothness can be produced.
• the coating amount of the coating solution in step A is preferably such that the film thickness of the coating film is 25 ⁇ m or more, more preferably 25 ⁇ m to 100 ⁇ m, and still more preferably 30 ⁇ m to 50 ⁇ m.
• the film thickness of the coating film is the film thickness of the coating film before the step B is performed, that is, before the drying.
• the film thickness of the coating film can be measured on the coating film immediately after coating using spectral interference method. Specifically, the film thickness of the coating film can be confirmed by "SI-T80" manufactured by Keyence Corporation.
• the coating method of the coating solution is not particularly limited, and can be performed by applying a known coating method.
• Examples of the coating method include known methods such as dip coating, air knife coating, curtain coating, roller coating, die coating, wire bar coating, and gravure coating.
• the coating solution is applied using a coating solution having a solid content concentration of 60% by mass or more (more preferably, the above solid content concentration), and a coating amount of 25 ⁇ m or more (more preferably, the above coating amount).
• the embodiment applied by the above is particularly preferred.
• the coating solution is applied using a coating solution having a solid content concentration of 60% by mass or more and a coating amount such that the film thickness of the coating film is 25 ⁇ m or more. The uneven distribution on the membrane surface is more effectively developed, and a film having better surface smoothness is obtained.
• the coating liquid used in step A has a value obtained by subtracting the surface tension shown when the solid concentration is 60 mass% from the surface tension shown when the solid concentration is 90 mass% is within 1 mN / m. Is preferred.
• the above “value obtained by subtracting the surface tension when the solid concentration is 60 mass% from the surface tension when the solid concentration is 90 mass%” is the same solid composition and the same solvent. It is a value calculated from surface tensions measured for two coating solutions having a solid content concentration of 90% by mass and 60% by mass, respectively.
• the surface tension of the coating solution is a value measured at 25 ° C. using a surface tension meter.
• FACE automatic surface tension meter CBVP-Z manufactured by Kyowa Interface Science Co., Ltd.
• the viscosity of the coating liquid at a liquid temperature of 25 ° C. is preferably 5 mPa ⁇ s to 50 mPa ⁇ s, more preferably 10 mPa ⁇ s to 40 mPa ⁇ s, and still more preferably 15 mPa ⁇ s to 30 mPa ⁇ s.
• the method of measuring the viscosity is as described above.
• the application of the coating solution in step A may be carried out on a sheet-like support or on a continuous support. If a continuous support is used, so-called roll-to-roll film production can be carried out.
• Step B Process B is twice as long as t seconds satisfying condition A shown below at a rate showing a mass change of 0.02 g / m 2 / s or more and 0.1 g / m 2 / s or less for the coated film formed in process A It is a process dried in time which becomes seconds or more. Drying in step B is drying that is positioned as initial drying.
• the dynamic surface tension ⁇ 1 with a bubble lifetime of 5 seconds when the dynamic surface tension ⁇ 1 with a bubble lifetime of 5 seconds has progressed to dryness in step B, the specific polymer contained in the coating liquid is in a state of being sufficiently unevenly distributed on the surface of the coating film It is a parameter
• the dynamic surface tension ⁇ 2 with a bubble lifetime t less than 5 seconds corresponds to the dynamic surface tension shown by the coating liquid in a state in which the dynamic surface tension ⁇ 1 has not been reached in the drying process of step B. It corresponds.
• step B in the present disclosure the relationship between the above-mentioned dynamic surface tensions ⁇ 1 and ⁇ 2 in controlling the drying conditions which can achieve a state in which the specific polymer contained in the coating liquid is sufficiently localized on the surface of the coating film Focus on ⁇ 2 / ⁇ 1 ⁇ 1.05), and show a mass change of 0.02 g / m 2 / s or more and 0.1 g / m 2 / s or less for a time that is twice or more seconds of t seconds satisfying this relationship
• the dynamic surface tension by the maximum bubble pressure method can be measured using a surface tension meter corresponding to the maximum bubble pressure method.
• a surface tension meter Specifically as a surface tension meter, SITA Pro line t15 (made by SITA Lab Solutions) etc. can be used.
• t seconds can be determined by calculating the number of seconds in which ⁇ 2 / ⁇ 1 ⁇ 1.05 from the power approximation curve of the plot obtained by changing the bubble lifetime from 15 ms to 10 seconds. Just do it.
• the drying time in step B is a time which is twice or more seconds of t seconds satisfying the condition A, preferably 2 to 20 seconds, and more preferably 2 to 10 seconds.
• the drying rate in the step B is a rate at which the coating film shows a mass change of 0.02 g / m 2 / s or more and 0.1 g / m 2 / s or less.
• the drying temperature in step B is not particularly limited and can be appropriately set according to the composition of the coating solution, preferably 25 ° C. to 60 ° C., more preferably 25 ° C. to 50 ° C., and still more preferably 25 ° C. to 40 ° C.
• drying means known drying means can be used, and examples thereof include known drying means such as heat drying, hot air drying, condensation drying and the like.
• Step C is a step of drying the coated film after step B at a rate showing a mass change of 0.02 g / m 2 / s or more and 0.2 g / m 2 / s or less. Step C is secondary drying performed after step B. In step C, in step B, the coating film in a state in which the specific polymer is unevenly distributed on the surface of the coating film is further dried.
• the drying rate in the step C is a rate showing a mass change of 0.02 g / m 2 / s or more and 0.2 g / m 2 / s or less.
• the drying rate in the step C is lower than the drying rate in the step B, as long as the coating film exhibits a mass change of 0.02 g / m 2 / s or more and 0.2 g / m 2 / s or less. It may be a large speed or a small speed.
• step B to step C is that the drying rate set in the range of mass change of 0.02 g / m 2 / s or more and 0.1 g / m 2 / s or less is 0.02 g / m 2 / It can judge by having been changed into another drying rate which shows mass change of s or more and 0.2 g / m ⁇ 2 > / s or less.
• the drying conditions of each drying zone are set to the conditions within the ranges of step B and step C, respectively. By doing this, it is possible to judge the transition from step B to step C.
• step B and step C are carried out using a single drying zone
• the drying conditions of the drying zone are in the range of step B to the range of step C.
• the change from step B to step C can be determined by the change.
• the process B and the process C may make a drying speed the same, and may implement them in series as the process B and the process C as the same process. In this case, step B doubles as step C.
• drying at a rate of less than 0.02 g / m 2 / s may be performed subsequent to step C.
• the drying time in the step C is not particularly limited, and may be a time until the drying rate of the coating film shows a mass change of less than 0.02 g / m 2 / s.
• the drying temperature in step C may be the same temperature as in step B, or may be a different temperature from step B.
• the drying temperature in step C is preferably 25 ° C. to 80 ° C., more preferably 25 ° C. to 70 ° C., and still more preferably 25 ° C. to 60 ° C.
• drying means in the step C the same drying means as in the step B can be mentioned.
• the manufacturing method of the present disclosure may have other steps other than the above-described step A, step B, and step C.
• processes such as a process (process D) of irradiating an active energy ray to a coating film, are mentioned.
• Step D When the coating liquid in the present disclosure is a coating liquid containing a polymerizable compound as a film-forming compound, the production method of the present disclosure preferably has a step (step D) of irradiating the coating film with active energy rays. Irradiation of active energy rays in step D is performed after step C (secondary drying).
• the active energy ray examples include active energy rays such as X-ray, electron beam, ultraviolet ray, visible light and infrared ray, and ultraviolet ray is preferable.
• active energy rays such as X-ray, electron beam, ultraviolet ray, visible light and infrared ray, and ultraviolet ray is preferable.
• the energy may be applied at one time, or may be divided and irradiated.
• irradiation in two or more separate steps, and at an initial low dose of 150 mJ / cm 2 or less It is preferable to irradiate ultraviolet rays, and then irradiate ultraviolet rays with a high irradiation amount of 50 mJ / cm 2 or more, and apply a high irradiation amount to the later stage than the initial stage.
• the surface smoothness of the film obtained by the production method of the present disclosure can be evaluated by using the ratio of the maximum height roughness Rz of the surface of the coating layer formed on the support to the film thickness h as an index.
• the specific evaluation method and evaluation means will be described in the examples described later.
• the hardness of the film obtained by the production method of the present disclosure is preferably 2H or more, more preferably 3H to 9H, and 4H to 8H. Is more preferred.
• the hardness of the film can be measured by a pencil hardness test in accordance with JIS K5600-5-4 (1999).
• the manufacturing method of the present disclosure can be implemented by a manufacturing apparatus having at least a coating unit and a drying unit.
• a manufacturing apparatus which can carry out the manufacturing method of the present disclosure, for example, an apparatus provided with a hot air dryer, a heater, or a condensing plate, a drying apparatus using hot air, and the like can be mentioned.
• the device described in Japanese Patent No. 4951301 can be suitably applied.
• the surface protection film with which a touch panel, an image display apparatus, etc. is equipped, the protective film for window glasses of a motor vehicle, etc. are mentioned.
• a resin base material can be used as a support body.
• a resin substrate on a film (hereinafter, also referred to as a resin film) can be used.
• the resin film may be a single-layer resin film, or may be a laminated film in which two or more resin films are laminated.
• the resin film may be obtained as a commercial product, or may be a resin film produced by a known film forming method.
• a resin film an acrylic resin film, a polycarbonate resin film, a polyolefin resin film, a polyester resin film, an acrylonitrile butadiene styrene copolymer (ABS) film, a triacetyl cellulose (TAC) film etc.
• the resin film includes at least one film selected from the group consisting of a triacetyl cellulose film, an acrylic resin film and a polycarbonate resin film, and a triacetyl cellulose film is more preferable.
• the resin film is a laminated film of two or more layers of resin films.
• the number of layers is, for example, two or three, but is not particularly limited.
• an acrylic resin film is a resin film containing the polymer or copolymer containing 1 or more types of monomer units selected from the group which consists of acrylic acid ester and methacrylic acid ester, for example, polymethacrylic acid A methyl resin (PMMA) film is mentioned.
• the thickness of the resin film is preferably in the range of 15 ⁇ m to 800 ⁇ m, more preferably in the range of 20 ⁇ m to 500 ⁇ m, and still more preferably in the range of 200 ⁇ m to 500 ⁇ m.
• the thickness of the resin film refers to the total thickness of the laminated film.
• the surface of the resin film may optionally be subjected to an adhesion promoting treatment such as corona discharge treatment by a known method.
• the coating solution contains a film forming compound.
• the film forming compound is a compound capable of forming a resin film, and includes both a polymerizable compound and a non-polymerizable resin.
• the film-forming compound is preferably a polymerizable compound from the viewpoint of producing a film having high hardness and surface smoothness.
• a polymerizable compound is a compound having a polymerizable group, and is a compound which itself causes a polymerization reaction upon application of an active energy ray, or is activated by receiving an active energy ray. It is a compound in which a polymerization reaction is induced by the action of components such as the polymerization initiator.
• the polymerizable compound may be a radically polymerizable compound or a cationically polymerizable compound. Both radically polymerizable compounds and cationically polymerizable compounds may be used in combination.
• the polymerizable compound may be a compound having one or more polymerizable groups in the molecule, and preferably has two or more polymerizable groups in the molecule.
• a polymerizable compound having three or more polymerizable groups in the molecule By using a polymerizable compound having three or more polymerizable groups in the molecule, a film having higher hardness can be produced.
• a preferred embodiment of the polymerizable compound is a compound having one or more (meth) acryloyl groups in the molecule, and a compound having three or more (meth) acryloyl groups in the molecule. Is more preferred.
• another preferable embodiment of the polymerizable compound is a compound having one or more epoxy groups in the molecule.
• Examples of the polymerizable compound include esters of polyhydric alcohol and (meth) acrylic acid, vinyl benzene and derivatives thereof, vinyl sulfone, (meth) acrylamide and the like.
• esters of polyhydric alcohol and (meth) acrylic acid are preferable.
• the polymerizable compound in addition to the compound having a (meth) acryloyl group, it is also preferable to use a compound having one or more epoxy groups in the molecule.
• numerator the compound represented by following General formula (1) is preferable.
• R represents a monocyclic hydrocarbon or a bridged hydrocarbon
• L represents a single bond or a divalent linking group
• Q represents an ethylenically unsaturated double bondable group or ring-opening polymerization Represents a sex group.
• L may be absent and R and Q may be directly bonded.
• the compound represented by following General formula (1A) or (1B) is more preferable, and the compound represented by following General formula (1A) with low molecular weight is still more preferable.
• the compound represented by the following general formula (1A) is also preferable for the isomer.
• R 1 represents a hydrogen atom or a methyl group
• L 2 represents a divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms.
• L 2 preferably has 1 to 3 carbon atoms, and more preferably 1 carbon atom (epoxycyclohexylmethyl (meth) acrylate).
• R 1 represents a hydrogen atom or a methyl group
• L 2 represents a divalent aliphatic hydrocarbon group having 1 to 3 carbon atoms.
• carbon number 1 is more preferable.
• a bivalent aliphatic hydrocarbon group a linear, branched or cyclic alkylene group is preferable, a linear or branched alkylene group is more preferable, and a linear alkylene group is still more preferable.
• JP-A-2017-95711 can be preferably applied as the polymerizable compound in the present disclosure.
• a commercial item may be used as a polymeric compound.
• a commercial product for example, KAYARD DPHA, PET-30 (above, Nippon Kayaku Co., Ltd.), NK ester A-TMMT, same A-TMPT (above, Shin-Nakamura Chemical Co., Ltd.), light ester 2EG (above) Kyoeisha Chemical Co., Ltd., Cyclomer M100 (Daicel Co., Ltd.) and the like can be mentioned.
• the molecular weight of the polymerizable compound is not particularly limited, but is preferably 600 or less, more preferably 360 or less, from the viewpoint of the hardness of the film. Further, from the viewpoint of suppressing volatilization at the time of film formation, the molecular weight of the polymerizable compound is preferably 80 or more, and more preferably 120 or more.
• the content of the polymerizable compound is preferably 80% by mass to 99% by mass, and 90% by mass to 98% by mass, with respect to the total solid content of the coating solution. It is more preferable that
• the coating solution may contain a non-polymerizable resin as a film forming compound.
• the non-polymerizable resin which may be contained in the coating solution of the present disclosure include cellulose acetate propionate and cellulose acetate butyrate.
• the content of the non-polymerizable resin may be set appropriately as long as the improvement effect of the surface smoothness in the present disclosure is not impaired.
• the content is preferably 0.5% by mass to 5% by mass, and more preferably 1% by mass to 3% by mass, with respect to the total solid content of the coating solution.
• the coating liquid is at least one selected from a polymer having a fluoroaliphatic group and a polymer having a siloxane structure, and the viscosity of a solution dissolved in methyl ethyl ketone at a solid content of 55% by mass is 15 mPa ⁇ s or more at 60 ° C. And a polymer (specific polymer). The details of the above-mentioned viscosity of the solution of the specific polymer are as described above.
• the polymer having fluoroaliphatic group means a polymer having at least one fluoroaliphatic group in the molecule.
• the fluoro aliphatic group means a group in which at least one of the hydrogen atoms of the aliphatic group is substituted by a fluorine atom.
• the fluoroaliphatic group is preferably a fluoroalkyl group, and more preferably a fluoroalkyl group having 1 or more carbon atoms.
• the fluoroalkyl group may be a perfluoroalkyl group.
• the fluoroalkyl group may have a substituent other than a fluorine atom.
• the polymer having a fluoroaliphatic group is preferably a polymer containing a repeating unit corresponding to the monomer represented by the following general formula 1.
• R 1 represents a hydrogen atom, a halogen atom or a methyl group.
• X represents an oxygen atom, a sulfur atom or -N (R 12 )-.
• R 12 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
• R f represents -CF 3 or -CF 2 H.
• Monomer represented by the general formula 1 (hereinafter, also referred to as monomer (i).)
• monomer (ii) monomer (i)
• R 1 represents a hydrogen atom, a halogen atom or a methyl group, preferably a hydrogen atom or a methyl group.
• X represents an oxygen atom, a sulfur atom or -N (R 12 )-, more preferably an oxygen atom or -N (R 12 )-, still more preferably an oxygen atom.
• R 12 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom or a methyl group.
• Rf represents -CF 3 or -CF 2 H.
• m represents an integer of 1 to 6, 1 to 3 is more preferable, and 1 is more preferable.
• n represents an integer of 1 to 11, 1 to 9 is more preferable, and 1 to 6 is more preferable.
• Rf is preferably -CF 2 H.
• polymer having a fluoroaliphatic group two or more types of constituent units corresponding to the fluoroaliphatic group-containing monomer represented by General Formula 1 may be contained.
• the monomer [monomer (ii)] represented by Formula 2 copolymerizable with the monomer (i) will be described.
• R 13 represents a hydrogen atom, a halogen atom or a methyl group, and a hydrogen atom or a methyl group is more preferable.
• Y represents an oxygen atom, a sulfur atom or -N (R 15 )-, more preferably an oxygen atom or -N (R 15 )-, still more preferably an oxygen atom.
• R 15 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group.
• R 14 represents a linear, branched or cyclic alkyl group having 1 to 60 carbon atoms, or an aromatic group (eg, a phenyl group or a naphthyl group).
• the alkyl group represented by R 14 may contain a poly (alkyleneoxy) group.
• the alkyl group represented by R 14 is preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and more preferably a linear or branched alkyl group having 1 to 10 carbon atoms.
• the amount of the monomer (i) used for producing the polymer having a fluoroaliphatic group is preferably 10% by mass or more based on the total amount of monomers of the polymer having a fluoroaliphatic group, more preferably Is 25% by mass or more, and more preferably in the range of 40% by mass to 90% by mass.
• polymer having a fluoroaliphatic group examples include the polymers exemplified in paragraph Nos. [0041] to [0046] of Japanese Patent No. 5933353, but the heavy polymer having a fluoroaliphatic group in the present disclosure can be mentioned. Coalescing is not limited to these.
• the weight average molecular weight of the polymer having a fluoroaliphatic group is preferably 3000 to 100,000, and more preferably 5,000 to 80,000.
• weight average molecular weight means a value measured by gel permeation chromatography (GPC).
• GPC gel permeation chromatography
• HLC registered trademark
• TSKgel registered trademark
• Super Multipore HZ-H as a column. It is possible to use THF (tetrahydrofuran) as an eluent using three 4.6 mm ID ⁇ 15 cm, Tosoh Corporation.
• the sample concentration is 0.45 mass%
• the flow rate is 0.35 ml / min
• the sample injection amount is 10 ⁇ l
• the measurement temperature is 40 ° C., using a differential refractive index (RI) detector .
• the standard curve is the standard sample TSK standard, polystyrene of Tosoh Corp .: “F-40”, “F-20”, “F-4”, “F-1”, “A-5000”, “A. It is made from eight samples of "-2500", "A-1000", and "n-propylbenzene".
• the polymer having a siloxane structure means a polymer having a siloxane bond (Si—O—Si bond) in its molecule as a partial structure.
• a polymer having a siloxane structure is used as the specific polymer, the viscosity of a solution having a solid content of 55% by mass in methyl ethyl ketone among the polymers having a siloxane structure is 15 mPa ⁇ s or more at a liquid temperature of 60 ° C.
• a commercial item may be used as a polymer which has a siloxane structure.
• Examples of commercially available products include X-22-174DX, X-22-2426, X22-164C and X-22-176D (all trade names) manufactured by Shin-Etsu Chemical Co., Ltd .; Toray Dow Corning SH200, L7604, FZ-2105, L-7604, Y-7006, SS-2801, and the like (all of which are trade names), and the like, but are not limited thereto.
• the content of the specific polymer in the coating solution is preferably 0.01% by mass to 3% by mass, and more preferably 0.03% by mass to 2, based on the total amount of the coating solution from the viewpoint of surface smoothness of the film. More preferably, it is 0.05% by mass to 1% by mass.
• the solvent is preferably selected from organic solvents which can dissolve or disperse the components contained in the coating solution.
• the solvent include alcohols such as methanol, ethanol, propanol, n-butanol and i-butanol; ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone and cyclohexanone; cellosolves such as ethyl cellosolve; toluene, xylene and the like Aromatics; glycol ethers such as propylene glycol monomethyl ether; acetates such as methyl acetate, ethyl acetate and butyl acetate; diacetone alcohol and the like.
• alcohols such as methanol, ethanol, propanol, n-butanol and i-butanol
• ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone and cyclohexanone
• cellosolves such as ethyl cellosolve
• a solvent may use only 1 type and may use 2 or more types together.
• two or more solvents it is preferable to combine them from the viewpoint of the drying speed and the solubility of the components of the coating solution.
• preferable combinations of solvents include a combination of cyclohexanone and methyl ethyl ketone, a combination of methyl ethyl ketone and methyl acetate, and the like. From the viewpoint of drying speed (slow drying), a combination of cyclohexanone and methyl ethyl ketone is more preferable.
• the content of the solvent in the coating solution can be appropriately adjusted within the range in which the coating suitability can be secured.
• the coating liquid in the present disclosure preferably has a solid content concentration of 60% by mass or more, and the content of the solvent in the coating liquid is contained in an amount such that the solid content concentration is 60% by mass or more Is preferred.
• the coating solution contains a polymerizable compound as a film forming compound, it is preferable to further contain a polymerization initiator.
• the polymerization initiator may be used alone or in combination of two or more.
• polymerization initiator commercially available compounds can be used.
• “Latest UV curing technology” p. 159, issuer; Kazuhiro Takata, Publisher; Co., Ltd., Technical Information Association, issued in 1991
• the compounds described in the BASF catalog can be used.
• any of a radical polymerization initiator and a cationic polymerization initiator may be used.
• alkylphenone photoinitiators for example, Irgacure 651, Irgacure 184, DAROCURE 1173, Irgacure 2959, Irgacure 127, DAROCURE MBF, Irgacure 907, Irgacure 369, Irgacure 379EG, etc.
• acyl phosphine oxide light A polymerization initiator (for example, Irgacure 819, LUCIRIN TPO), others (for example, Irgacure 784, Irgacure OXE0, Irgacure OXE02, Irgacure 754) and the like can be used.
• Each of the exemplified compounds in parentheses is a radical polymerization initiator manufactured by BASF.
• the content of the radical polymerization initiator is preferably in the range of 0.1% by mass to 10% by mass, preferably 1% by mass to 5% by mass, based on 100% by mass of the total solid content of the coating liquid. % To 4% by mass is more preferable.
• a cationic polymerization initiator known compounds such as a photoinitiator of photo cationic polymerization, a photo decolorizing agent of dyes, a photo-discoloring agent, or a known acid generator used for a micro resist or the like and those A mixture etc. are mentioned.
• a cationic polymerization initiator an onium compound, an organic halogen compound, and a disulfone compound are mentioned, for example.
• the organic halogen compound and the disulfone compound the same ones as described in the above compounds which generate a radical can be mentioned.
• onium compounds examples include diazonium salts, ammonium salts, iminium salts, phosphonium salts, iodonium salts, sulfonium salts, arsonium salts, selenonium salts, etc.
• diazonium salts ammonium salts
• iminium salts iminium salts
• phosphonium salts phosphonium salts
• iodonium salts sulfonium salts
• arsonium salts arsonium salts
• selenonium salts etc.
• an onium salt is mentioned, and a diazonium salt, an iodonium salt, a sulfonium salt, an iminium salt is preferable from the viewpoint of the photosensitivity of photopolymerization start, the material stability of a compound, etc. Most preferred are iodonium salts in terms of sex.
• the onium salt which can be suitably used, for example, an amylated sulfonium salt described in paragraph [0035] of JP-A-9-268205, paragraph [#] of JP-A-2000-71366.
• Diaryl iodonium salts or triaryl sulfonium salts described in 0010] to [0011] sulfonium salts of thiobenzoic acid S-phenyl ester described in paragraph [0017] of JP-A-2001-288205, JP-A-2001-133696
• the onium salts described in paragraph Nos. [0030] to [0033] of the gazette the onium salts described in paragraph Nos. [0030] to [0033] of the gazette.
• organometallic / organic halides described in paragraph Nos. [0059] to [0062] of JP-A-2002-29162, a photoacid generator having an o-nitrobenzyl type protective group, and photolysis. And compounds such as iminosulfonates and the like that generate sulfonic acid.
• iodonium salt-based cationic polymerization initiator examples include B2380 (manufactured by Tokyo Chemical Industry Co., Ltd.), BBI-102 (manufactured by Midori Kagaku), WPI-113 (manufactured by Wako Pure Chemical Industries, Ltd.), WPI-124 (Wako Pure Chemical Industries, Ltd.) Industrial), WPI-169 (Wako Pure Chemical Industries), WPI-170 (Wako Pure Chemical Industries), DTBPI-PFBS (Toyosei Chemical), DTBPI-CS (Toyosei Chemical), PI-2074 Rhodia Japan) or the like can be used.
• a cationic polymerization initiator As a cationic polymerization initiator, only 1 type may be used and 2 or more types may be used together.
• the cationic polymerization initiator is preferably in the range of 0.1% by mass to 10% by mass, and more preferably 0.3% by mass to 3.0%, based on 100% by mass of the total solid content of the coating solution. It is mass%.
• the coating liquid may contain other components other than those described above, as needed. As other components, a polymerization inhibitor, an ultraviolet absorber, etc. are mentioned.
• Irg 184 alkylphenone photopolymerization initiator (BASF)
• CPI-100P Photocationic polymerization initiator, triarylsulfonium salt (San Apro Co., Ltd.)
• the solid content concentrations of the coating liquids A-1 to A-9 obtained above and the viscosity at a liquid temperature of 25 ° C. are shown in Table 3 or Table 4 below.
• the viscosity in 25 degreeC of liquid temperature of the solution (solid content 55 mass%) which melt
• sample solutions are prepared, each having a solid content concentration adjusted to 90% by mass or 60% by mass, with the same solid composition as that of the coating liquids A-1 to A-9 and the solvent amount changed.
• the surface tension was measured by the method described above.
• a value obtained by subtracting the surface tension of a sample liquid having a solid content concentration of 60 mass% was calculated from the surface tension of a sample liquid having a solid content concentration of 90 mass%. The results are shown in Table 3 or Table 4.
• Coating of Coating Solution Coating amount of each coating solution obtained above on the support (triacetyl cellulose (TAC) film, thickness: 120 ⁇ m) is the coating amount to obtain the film thickness described in Table 3 or Table 4. It apply
• Step B> The coated film formed on each support was subjected to step B (initial drying) under the drying conditions (drying speed and drying time) shown in Table 3 or Table 4.
• the drying time shown in Table 3 or Table 4 was set as a drying time which is twice or more seconds of “t seconds” obtained by the following.
• the bubble lifetime was measured up to 5000 ms using a SITA Pro line t15 (manufactured by SITA Lab Solutions) at a solution temperature of 25 ° C. to obtain a dynamic surface tension ⁇ 1.
• a hot air dryer manufactured by Yamato Scientific Co., Ltd., Clean Oven DE42 was used.
• Step C secondary drying was subsequently performed on the coated film after step B (initial drying) under the drying conditions (drying speed and drying time) shown in Table 3 or Table 4.
• the drying means was the same as step B.
• Step D> The coating film after the step C was irradiated with ultraviolet light at an illuminance of 400 mW / cm 2 and an irradiation amount of 1000 mJ / cm 2 under a condition of nitrogen 0.1 ppm or less to cure the coating film.
• Example 12 A die coater as described in Example 1 of JP-A-2006-122889 on a support which was unrolled from a support roll (Triacetis cellulose (TAC) film roll, Fuji Film Co., Ltd., thickness: 120 ⁇ m).
• TAC Triacetis cellulose
• the coating solution A-1 is applied at a transfer speed of 10 m / min to form a coating film (step A), and the coating film formed is subjected to the drying temperature and drying time shown in Table 3 or Table 4 using After drying (steps B and C), after drying, the coated film is irradiated with ultraviolet light at an illuminance of 400 mW / cm 2 and an irradiation amount of 1000 mJ / cm 2 under the condition of an oxygen concentration of about 0.1 ppm or less under nitrogen purge. After curing (step D), it was wound up.
• the film of Example 12 was manufactured by the above.
• the hardness measured according to the above-described pencil hardness test for the surface on the resin film side of each film obtained in the examples was in the range of 4H to 8H.
• the roughness curve was measured using a high-precision fine shape measuring instrument Surfcorder ET4000A (Kosaka Research Institute), and the maximum height roughness Rz was calculated.
• the film thickness h of the resin film of each evaluation sample was measured using a spectral reflection film thickness meter FE-3000 (Otsuka Electronics Co., Ltd.).
• the ratio (Rz / h) of the obtained maximum height roughness Rz to the film thickness h was calculated, and the surface condition was evaluated according to the following evaluation criteria. Evaluation ranks A and B are levels at which there is no problem in practical use, and evaluation rank A indicates that the surface smoothness is more excellent.
• a water-dispersible pressure-sensitive adhesive composition was prepared by blending 0.07 parts by mass of TETRAD-C, manufactured by Mitsubishi Gas Chemical Co., Ltd.).
• a release sheet / adhesive layer is obtained by laminating this adhesive layer and a release-treated surface of another release sheet (Lintech Co., Ltd., trade name: SP-PET 3801) in which one side of the polyethylene terephthalate film is release-treated with a silicone release agent.
• a pressure-sensitive adhesive sheet was produced, which was laminated in the order of:
• the films obtained by the manufacturing method of the examples all have surface evaluation of A or B, and it is understood that the films are excellent in surface smoothness.
• the drying time of the initial drying (step B) is outside the range of the manufacturing method of the present disclosure
• the drying speed of the initial drying (step B) is outside the range of the manufacturing method of the present disclosure.
• Comparative Examples 2 and 3 Comparative Example 4 in which the drying speed of the secondary drying (step C) is out of the range of the manufacturing method of the present disclosure, and comparison in which the MEK solution viscosity of the specific polymer is out of the range of the manufacturing method of the present disclosure It is understood that in Example 5 and Comparative Example 5 in which the specific polymer is not used, the surface state evaluation is inferior and the desired surface smoothness is not obtained.

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